2,2-dimethylpropanediol-1,3-dinitrite

ABSTRACT

NITRITES OF GLYCOLS AND GLYCOL DERIVATIVES OBTAINABLE BY ESTERIFICATION WITH NITROUS ACID. THE COMPOUNDS ARE EMINENTLY SUITABLE AS DIAZOTIZING AGENTS, PARTICULARLY IN ORGANIC SOLUTION.

United States Patent 3,792,077 2,2-DIMETHYLPROPANEDIOL-1,3-DINITR1TE Rudolf Bermes, Ludwigshafen, and Karl Schmeidl,

Frankenthal, Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen am Rhine, Germany No Drawing. Filed Oct. 4, 1971, Ser. No. 186,513 Claims priority, application Germany, Sept. 4, 1971, P 21 44 420.2 Int. Cl. C07c 77/02 US. Cl. 260467 1 Claim ABSTRACT OF THE DISCLOSURE Nitrites of glycols and glycol derivatives obtainable by esterification with nitrous acid. The compounds are eminently suitable as diazotizing agents, particularly in organic solution.

The invention relates to compounds having the 'Formula Ia or 1 h R ONO-(KJJHCH2O)DX or 0NOR ONO a) in which R denotes hydrogen or methyl, R denotes a linear or branched alkylene radical having four to nine carbon atoms, X denotes alkyl, phenyl, acetyl or NO, and n denotes 2 or 3 with the proviso that n is also 1 when X denotes alkyl, phenyl or acetyl.

Examples of alkylene radicals R are:

-(CHz)4, -(CHz) 5-, -(CHz)s-, CHzCHCHz-,

Examples of alkyl radicals X are methyl, ethyl, propyl or butyl.

Examples of compounds having the Formula Ia are the nitrites of the following compounds:

CH O-CHgCHz-OH CzH50-CH2CH2-OH CaH1OCH2CHz-OH C4HnO-CH2CH2OH Ho--(oH 0H2o)2H HO-(CHzCHz0)aH CHaO (CHgCHzOhH CH3 CHaO-CHz-CH-OH CH CHgO-(CH-CHzOhH CH3 C2H O(CH-OH2O):H

CHaCOOCHzCHaOH 051150 CHzCHzOH CgHsO (CHzCHzO)zH C H(CHzCH O)gH 4 oO( 2CH2O)zH CHaO(CHzCHzO) H C H5O(CHzCHzO)aH C H7O CH2CH2O)3H 041100 (CH2CH20)3H 3,792,077 Patented Feb. 12, 1974 In order to prepare compounds having the Formula Ia or Ib, the corresponding hydroxy compounds (commercial purity being adequate) may be esterified with nitrous acid or oxides of nitrogen by known methods. Details of the production are described in the examples.

Compounds having the Formula II:

R ONO-(CH-CHzOhY (I in which Y denotes alkyl having one to four carbon atoms, acetyl or NO, and

R and n have the meanings given above, are of particular industrial importance.

Individual preferred compounds are the nitrites of the following diols and diol hemiethers:

EXAMPLE 1 591 parts of glycol monobutyl ether is stirred with 500 parts of ice and 345 parts of sodium nitrite. Then While continuing the stirring 632 parts of about 30% hydrochloric acid is allowed to flow in beneath the surface at a moderate rate. The temperature is prevented from rising above 10 C. by external cooling. The nitrite separates out and is drawn oif from the aqueous phase in a separating funnel. 714 parts of butyl glycol nitrite (97% of the theory) is obtained. It is washed successively with water and dilute sodium carbonate solution and dried over sodium sulfate. Refractive index n =l.4025.

EXAMPLE 2 671 parts of dipropylene glycol is stirred with 1000 parts of ice and 690 parts of sodium nitrite. While stirring well, 1265 parts of about 30% hydrochloric acid is run in fairly quickly beneath the surface of the mixture. The temperature is kept below 5 C. by external cooling. Stirring is continued for a few minutes, the lighter product phase is separated in a separating funnel and 908 parts (94% of theory) of dipropylene dinitrite is obtained and is washed with ice-water and sodium bicarbonate solution and dried over sodium sulfate. Refractive index n;;: 1.4110.

EXAMPLE 3 521 parts of 2,2-dimethylpropanediol-1,3 is dissolved in 500 parts of water and stirred with 500 parts of ice and 690 parts of sodium nitrite. 1265 parts of about 30% hydrochloric acid is then stirred in below the surface with external cooling so that the temperature does not rise above 5 C. Stirring is continued for another ten minutes and the organic phase is separated from the aqueous phase in a separating funnel. 800 parts (98% of the theory) of the dinitrite of 2,2-dimethylpropanediol-1,3 is obtained.

The product is washed with water and dried successively over anhydrous sodium carbonate and sodium sulfate.

Refractive index n =1.4070.

When the hydroxy compounds set out in the following table are used and a procedure analogous to that in Examples 1 to 3 is followed, corresponding nitrites are obta1ned:

Refractive index of the Measured Example number Hydroxy compound (di)nitrite at C.

HOCHzCH2OCHa l. 3790 23 5. HOCHzCHzOCzHs 1. 3884 22 6 HO CHzCHzO CzH1 1. 3925 2G 7 HO OHzCHzO CaHs 1. 5062 22 8 HO CHZOHZOCOCH: 1. 4040 23 9 HO (CH2CH20)zH 1. 4068 26 10- HO (CH2CH2O)2CH3 1. 4075 21 11. HO (CH2CH20)2C2H5 1. 4112 22 12...- HO (CH2CH2O)2C3H1 1. 4111 26 13 HO (CH2CH20)2C4Hn 1. 4182 22 14 HO (CHzCHzOhH 1. 4242 22 15 HO (CHzCH20)aCHs 1. 4188 26 16 HO (CHzCHzOhCtHa 1. 4202 26 17 HO (CH2CH20)3C3H1 1. 4222 26 18 HO (CH2CH2O) C4H9 1. 4265 22 19 HO (CH H 1. 4055 25 20..-- HO (CH2)5OH 1.4115 21 21 HO (CHmOH 1. 4155 23 22 CzHa 1. 4348 20 H O C H26 C Hz 0 H Refractive index of the Measured Example number Hydroxy compound (di)nitrite at HO CH2-l--C HOH CH3 C3H1 H O 0 H2 0 H C H O H We claim: 1. The compound of the formula ONO-CHr-(E-CHr-ONO References Cited Kuhn et al., J. Am. Chem. Soc., vol. 78, pp. 2719- LELAND A. SEBASTIAN, Primary Examiner US. Cl. X.R. 260-466 

